EP3750848B1 - Method for preparing lithium bis(fluorosulfonyl)imide salt - Google Patents
Method for preparing lithium bis(fluorosulfonyl)imide salt Download PDFInfo
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- EP3750848B1 EP3750848B1 EP19785468.0A EP19785468A EP3750848B1 EP 3750848 B1 EP3750848 B1 EP 3750848B1 EP 19785468 A EP19785468 A EP 19785468A EP 3750848 B1 EP3750848 B1 EP 3750848B1
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- Prior art keywords
- fluorosulfonyl
- imide salt
- lithium bis
- reaction solution
- lithium
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- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical class [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 title claims description 97
- 238000000034 method Methods 0.000 title claims description 46
- 238000006243 chemical reaction Methods 0.000 claims description 86
- 239000003960 organic solvent Substances 0.000 claims description 46
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 33
- PVMUVDSEICYOMA-UHFFFAOYSA-N n-chlorosulfonylsulfamoyl chloride Chemical compound ClS(=O)(=O)NS(Cl)(=O)=O PVMUVDSEICYOMA-UHFFFAOYSA-N 0.000 claims description 22
- -1 polypropylene Polymers 0.000 claims description 20
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 19
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- 239000007790 solid phase Substances 0.000 claims description 17
- 239000011521 glass Substances 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 16
- 238000010992 reflux Methods 0.000 claims description 16
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- 239000004743 Polypropylene Substances 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- 229920001155 polypropylene Polymers 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- 229910001868 water Inorganic materials 0.000 claims description 8
- 229920001903 high density polyethylene Polymers 0.000 claims description 7
- 239000004700 high-density polyethylene Substances 0.000 claims description 7
- AZVCGYPLLBEUNV-UHFFFAOYSA-N lithium;ethanolate Chemical compound [Li+].CC[O-] AZVCGYPLLBEUNV-UHFFFAOYSA-N 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- 229920001774 Perfluoroether Polymers 0.000 claims description 3
- 150000008064 anhydrides Chemical class 0.000 claims description 3
- MSKQYWJTFPOQAV-UHFFFAOYSA-N fluoroethene;prop-1-ene Chemical group CC=C.FC=C MSKQYWJTFPOQAV-UHFFFAOYSA-N 0.000 claims description 3
- JILPJDVXYVTZDQ-UHFFFAOYSA-N lithium methoxide Chemical compound [Li+].[O-]C JILPJDVXYVTZDQ-UHFFFAOYSA-N 0.000 claims description 3
- LZWQNOHZMQIFBX-UHFFFAOYSA-N lithium;2-methylpropan-2-olate Chemical compound [Li+].CC(C)(C)[O-] LZWQNOHZMQIFBX-UHFFFAOYSA-N 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- 239000000243 solution Substances 0.000 description 53
- 239000000047 product Substances 0.000 description 30
- 238000002360 preparation method Methods 0.000 description 23
- 238000004293 19F NMR spectroscopy Methods 0.000 description 12
- 238000007086 side reaction Methods 0.000 description 11
- 239000007787 solid Substances 0.000 description 10
- 238000001228 spectrum Methods 0.000 description 10
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000013078 crystal Substances 0.000 description 8
- 239000010410 layer Substances 0.000 description 8
- 239000012071 phase Substances 0.000 description 8
- 229910052744 lithium Inorganic materials 0.000 description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 229910001290 LiPF6 Inorganic materials 0.000 description 3
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 150000007514 bases Chemical class 0.000 description 2
- 238000005341 cation exchange Methods 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000004334 fluoridation Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910014276 N-Li Inorganic materials 0.000 description 1
- 229920002274 Nalgene Polymers 0.000 description 1
- 229910014326 N—Li Inorganic materials 0.000 description 1
- 229910005948 SO2Cl Inorganic materials 0.000 description 1
- 229910006095 SO2F Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- WEVYAHXRMPXWCK-FIBGUPNXSA-N acetonitrile-d3 Chemical compound [2H]C([2H])([2H])C#N WEVYAHXRMPXWCK-FIBGUPNXSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000005293 duran Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000000806 fluorine-19 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002641 lithium Chemical group 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000011356 non-aqueous organic solvent Substances 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
- C01B21/086—Compounds containing nitrogen and non-metals and optionally metals containing one or more sulfur atoms
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to a method for preparing a lithium bis(fluorosulfonyl)imide salt, and more particularly, to a method for preparing a lithium bis(fluorosulfonyl)imide salt, which is carried out in one-step reaction to improve processability, and in a vessel of a specific material suppressing side reactions to improve production efficiency.
- electrolytes of lithium secondary batteries ion conductive nonaqueous electrolytes obtained by dissolving electrolyte salts in nonaqueous organic solvents are primarily used.
- a lithium salt such as LiPF 6 which is widely used as the electrolyte salt is a material having low thermal stability and moisture sensitivity, and in case of reacting with water, HF is produced as a by-product due to the hydrolysis of PF 6 - .
- the HF thus produced spontaneously reacts with an electrode active material which shows weak basicity, to elute an electrode active material component. More particularly, if a positive electrode active material reacts with HF, a positive electrode active material component is eluted, of course, and lithium fluoride (LiF) is formed on the surface of the positive electrode to increase electrical resistance in an electrode and generate gas, thereby degrading battery life.
- LiPF 6 lithium fluoride
- LiFSI lithium bis(fluorosulfonyl)imide salt
- the lithium bis(fluorosulfonyl)imide salt may be prepared via (1) fluoridating reaction of chlorosulfonyl imide or the salt thereof, (2) cation exchange reaction, and (3) contact reaction with an aqueous alkaline solution, in order. Accordingly, the preparation method is a multistep synthetic process and complicated, and thus, the commercialization thereof is difficult considering cost competition when compared with LiPF 6 .
- the yield of the lithium bis(fluorosulfonyl)imide salt is also lower when compared with the conventional lithium salts, and the development of a method for preparing a lithium bis(fluorosulfonyl)imide salt with high purity while decreasing the cost for the occupation of the market, is required.
- Patent Document Korean Patent Laid-open Publication No. 2012-0022833
- CN 106 276 829 A relates to a method for preparing lithium bis(fluorosulfonyl) imide (LiFSI) which comprises dissolving bis(chlorosulfonyl)imide in ethyl acetate and the addition of lithium fluoride.
- LiFSI lithium bis(fluorosulfonyl) imide
- JP 2018-035054 A describes the preparation of a bis(fluorosulfonyl)imide alkali metal salt by reacting a mixture of bis(fluorosulfonyl) and lithium fluoride.
- EP 2 578 533 A1 discloses the preparation of an alkali metal salt of a fluorosulfonyl imide by fluorination of a chlorosulfonyl imide and concentration of the reaction solution while bubbling gas thereinto or by thin film distillation.
- An aspect of the present invention to solve the above-described problems is to provide a method for preparing a lithium bis(fluorosulfonyl)imide salt with high purity, by which reaction steps are simplified and side reactions are minimized.
- a method for preparing a lithium bis(fluorosulfonyl)imide salt including a step of dissolving bis(chlorosulfonyl)imide in an organic solvent in a non-glass vessel to prepare a first reaction solution; a step of injecting lithium fluoride (LiF) to the first reaction solution in the non-glass vessel and refluxing while heating to prepare a second reaction solution; a step of separating a product including a lithium bis(fluorosulfonyl)imide salt and the organic solvent from the second reaction solution; and a step of obtaining the lithium bis(fluorosulfonyl)imide salt in a solid phase from the product, wherein the organic solvent is at least one or more selected from the group consisting of ethyl acetate, butyl acetate, chloroform, dichloromethane, dichloroethane, benzene, xylene and acetonitrile, wherein
- the step of separating the product from the second reaction solution may include a step of cooling the second reaction solution; and a step of injecting an extractor to the cooled second reaction solution to separate the product including the lithium bis(fluorosulfonyl)imide salt and the organic solvent.
- the step of obtaining the lithium bis(fluorosulfonyl)imide salt in a solid phase from the product may include a step of removing the organic solvent from the product for concentration; and a step of drying the concentrated product to obtain the lithium bis(fluorosulfonyl)imide salt in a solid phase.
- the organic solvent may be used in from 200 parts by weight to 1,000 parts by weight with respect to 100 parts by weight of the bis(chlorosulfonyl)imide.
- the lithium fluoride (LiF) may be injected in 1 mol to 10 mol with respect to 1 mol of the bis(chlorosulfonyl)imide.
- a time period for the refluxing while heating may be from 2 hours to 20 hours.
- the extractor may include at least one or more selected from the group consisting of LiOH (anhydride), LiOH ⁇ H 2 O, Li 2 CO 3 , lithium methoxide (LiOMe), lithium ethoxide (LiOEt) and lithium tert-butoxide (LiOt-Bu).
- the method for preparing a lithium bis(fluorosulfonyl)imide salt according to the present invention may simplify a synthesis process to improve processability when compared with the conventional process, and may save production costs.
- the synthesis reaction is performed in a non-glass vessel, side reactions generated during the reaction in a glass vessel during synthesis reaction may be prevented from happening, and a lithium bis(fluorosulfonyl)imide salt with high purity may be prepared.
- FIG. 1 is a 19 F-NMR spectrum of a lithium bis(fluorosulfonyl)imide salt prepared in Example 1 of the present invention.
- the method for preparing a lithium bis(fluorosulfonyl)imide salt according to the present invention includes (1) a step of dissolving bis(chlorosulfonyl)imide in an organic solvent in a non-glass vessel to prepare a first reaction solution, (2) a step of injecting lithium fluoride (LiF) to the first reaction solution in the non-glass vessel and refluxing while heating to prepare a second reaction solution, (3) a step of separating a product including a lithium bis(fluorosulfonyl)imide salt and the organic solvent from the second reaction solution, and (4) a step of obtaining the lithium bis(fluorosulfonyl)imide salt in a solid phase from the product.
- LiF lithium fluoride
- the organic solvent may be at least one or more selected from the group consisting of ethyl acetate, butyl acetate, chloroform, dichloromethane, dichloroethane, benzene, xylene and acetonitrile.
- each step will be explained in detail.
- the step for preparing the first reaction solution is conducted by dissolving bis(chlorosulfonyl)imide in an organic solvent in a non-glass vessel.
- the present invention creates a method for preparing a lithium bis(fluorosulfonyl)imide salt in a solid phase with high purity, by which a first reaction solution is prepared in a non-glass vessel and lithium fluoride (LiF) is directly injected into the vessel, and thus, reaction steps are simplified, and side reactions of lithium fluoride (LiF) with silicon (Si) included in a vessel of a glass material is prevented from happening.
- the non-glass vessel is formed using at least one or more materials selected from the group consisting of polypropylene (PP), polytetrafluoroethylene (PTFE), high-density polyethylene (HDPE), a perfluoroalkoxy resin (PFA), polyvinylidene difluoride (PVDF), and fluoroethylene propylene (FEP).
- PP polypropylene
- PTFE polytetrafluoroethylene
- HDPE high-density polyethylene
- PFA perfluoroalkoxy resin
- PVDF polyvinylidene difluoride
- FEP fluoroethylene propylene
- the organic solvent which is the solvent of the first reaction solution may use any solvents which is capable of dissolving bis(chlorosulfonyl)imide without inducing side reactions with the bis(chlorosulfonyl)imide, typically, at least one or more selected from the group consisting of ethyl acetate, butyl acetate, chloroform, dichloromethane, dichloroethane, benzene, xylene and acetonitrile may be used.
- organic solvent an organic solvent such as tetrahydrofuran (THF) and toluene is not used, because these solvents may participate in the reaction and induce side reactions, and may inhibit the substitution reaction of the bis(chlorosulfonyl)imide and hinder the production of a lithium bis(fluorosulfonyl)imide salt.
- the organic solvent may be included in 200 parts by weight to 1,000 parts by weight, preferably, 300 parts by weight to 700 parts by weight, more preferably, 300 parts by weight to 500 parts by weight with respect to 100 parts by weight of the bis(chlorosulfonyl)imide.
- the time period of the step for preparing the first reaction solution is set to a time period for sufficiently dissolving the bis(chlorosulfonyl)imide in the organic solvent without precipitation, and the first reaction solution may be prepared within 10 hours or less, more particularly, from 10 minutes to 2 hours.
- the second reaction solution is prepared by injecting lithium fluoride (LiF) in a non-glass vessel in which the first reaction solution has been prepared, and refluxing while heating.
- LiF lithium fluoride
- a chlorine atom (Cl) of the bis(chlorosulfonyl)imide may be substituted with a fluorine atom (F) of lithium fluoride (LiF) by heat.
- the lone pair of a nitrogen atom (N) contained in the bis(chlorosulfonyl)imide reacts with a lithium atom (Li) of lithium fluoride (LiF) to produce a lithium bis(fluorosulfonyl)imide salt.
- the hydrogen of the bis(chlorosulfonyl)imide and the fluorine of the lithium fluoride (LiF) may partially react to produce hydrogen fluoride (HF).
- the second reaction solution is prepared.
- the lithium fluoride (LiF) may be included in 1 mol to 10 mol, preferably, 1.8 mol to 10 mol, more preferably, 1.9 mol to 10 mol with respect to 1 mol of the bis(chlorosulfonyl)imide. If an excessive amount of the lithium fluoride (LiF) remains after finishing the reaction, side reactions may be induced and the lithium fluoride (LiF) is required to be removed after finishing the reaction. However, the removal of remaining lithium fluoride is a difficult process and costs high.
- the lithium fluoride (LiF) is preferably in the range to perform sufficient reaction of the bis(chlorosulfonyl)imide, and to minimize the amount of remaining lithium fluoride (LiF) after finishing the reaction, thereby preventing side reactions from happening and increasing processability and reaction efficiency.
- the refluxing heating process may be performed while keeping the temperature to the boiling point of the organic solvent used or higher for from 2 hours to 20 hours, particularly, from 5 hours to 20 hours, more particularly, from 5 hours to 15 hours.
- the temperature conditions of the refluxing heating process may be changed according to the kind of the organic solvent used, and if the refluxing heating process is carried out in the time period range, the reaction may be sufficiently carried out, and the production of by-products due to side reactions may be prevented.
- a product including the lithium bis(fluorosulfonyl)imide salt and the organic solvent is separated from the second reaction solution.
- the step of separating the product from the second reaction solution includes 1) a step of cooling the second reaction solution and 2) a step of injecting an extractor to the cooled second reaction solution to separate the product including the lithium bis(fluorosulfonyl)imide salt and the organic solvent.
- the cooling step is a step for cooling the second reaction solution after finishing the reaction to room temperature or less, so that additional side reactions may not arise due to remaining heat after finishing the refluxing heating process, which is performed for the preparation of the second reaction solution.
- the room temperature means the annual mean temperature or the atmospheric temperature, particularly, the temperature in a range of 20 ⁇ 5°C.
- the separating step of the product is a step of injecting an extractor to the cooled second reaction solution, and is a step of neutralizing the second reaction solution which is in a strongly acidic state as well as removing hydrogen fluoride (HF) produced as by-products during carrying out the reaction, and of separating the product including the lithium bis(fluorosulfonyl)imide salt and the organic solvent.
- HF hydrogen fluoride
- a lithium-containing basic compound may be used, and typical examples may include at least one or more selected from the group consisting of LiOH (anhydride), LiOH ⁇ H 2 O, Li 2 CO 3 , lithium methoxide (LiOMe), lithium ethoxide (LiOEt) and lithium tert-butoxide (LiOt-Bu).
- LiOH anhydride
- LiOMe lithium methoxide
- LiOEt lithium ethoxide
- LiOt-Bu lithium tert-butoxide
- the extractor may be included in 1 mol to 10 mol, preferably, 2 mol to 7 mol, more preferably, 3 mol to 6 mol with respect to 1 mol of the bis(chlorosulfonyl)imide. If the extractor in included in the range, a strongly acidic reaction solution may be neutralized, and impurities may be removed to produce a product with high purity.
- the hydrogen fluoride (HF) may be neutralized and separated from the product including the lithium bis(fluorosulfonyl)imide salt and the organic solvent, and may be easily removed in a subsequent extracting step of the organic solvent.
- the reaction solution is stirred at a temperature of room temperature or less, particularly, under temperature conditions of -10°C to 10°C for 30 minutes to 3 hours, the lithium bis(fluorosulfonyl)imide salt may be extracted by an organic solvent.
- the compound produced as by-products reacts with hydrogen fluoride (HF) to produce an insoluble salt, and an organic layer may be separated through filtering.
- HF hydrogen fluoride
- the second reaction solution into which the extractor is injected is injected into a separating funnel, an organic solvent layer including the product and an aqueous layer in which hydrogen fluoride (HF) and the extractor are dissolved, are separated, and the separated organic solvent layer may be recovered.
- HF hydrogen fluoride
- the step of obtaining the lithium bis(fluorosulfonyl)imide salt in a solid phase from the product will be explained.
- 1) a step of removing the organic solvent from the product for concentration, and 2) a step of drying the concentrated product to obtain a lithium bis(fluorosulfonyl)imide salt in a solid phase are included.
- Step 1) and step 2) both are steps for improving the yield of the lithium bis(fluorosulfonyl)imide salt in a solid phase
- step 1) is a step for removing the organic solvent from the product.
- a method of concentrating at a low temperature in a reduced pressure, or a method of distilling by heating in an atmospheric pressure may be applied.
- the method is not limited to the illustrated methods, and any methods for improving the yield of the lithium bis(fluorosulfonyl)imide salt in a solid phase may be used as long as side reactions with the product are not induced and the organic solvent may be removed.
- the step of drying the product concentrated after step 1) is a step of drying the product in vacuum or in an environment blocked from the air. Drying processes generally used may be applied, and for example, a method of drying by applying heat in vacuum or a method of drying in a sealed desiccator may be used. Through the drying step, the lithium bis(fluorosulfonyl)imide salt in a solid phase may be obtained.
- the yield of the lithium bis(fluorosulfonyl)imide salt was only 160 or less by the conventional preparation method of the lithium bis(fluorosulfonyl)imide salt, but by using the method of the present invention, the lithium bis(fluorosulfonyl)imide salt in a solid phase may be obtained in a yield of at least 210 or higher.
- lithium fluoride (1.21 g, 46.8 mmol) was injected while stirring the first reaction solution at room temperature, and in a sealed state, refluxing while heating was carried out for 6 hours to prepare a second reaction solution.
- the second reaction solution was cooled to room temperature (25°C), and a saturated LiOH ⁇ H 2 O aqueous solution (about 25 w/v%, 20 mL, 119 mmol) was added thereto dropwisely as an extractor while stirring, and the resultant solution was stirred for 30 minutes at a temperature or room temperature or less (-10°C to 15°C).
- the second reaction solution containing the extractor was poured to a separating funnel to separate an organic solvent layer containing the product and an aqueous layer containing hydrogen fluoride (HF).
- the organic solvent layer thus separated was recovered.
- the organic solvent layer thus recovered was concentrated in reduced pressure conditions until obtaining a semi-solid state.
- an organic solvent layer residue in the semi-solid state was dried further in vacuum at room temperature for 1 hour or more to obtain a lithium bis(fluorosulfonyl)imide salt (yield 25%) in a white crystal phase.
- the lithium bis(fluorosulfonyl)imide salt thus obtained was identified by 19 F-NMR ( 19 F-NMR (470 MHz, CD 3 CN): ⁇ 51.062 (s)) (see FIG. 1 ), and as a result, the purity was 99% or more and impurities were not found.
- a lithium bis(fluorosulfonyl)imide salt (yield 210) in a white crystal phase was obtained by the same method described in Example 1 except for using acetonitrile (20 mL, 15.7 g) as the organic solvent during preparing the first reaction solution.
- the lithium bis(fluorosulfonyl)imide salt thus obtained was identified by 19 F-NMR, and the same spectrum as in Example 1 was obtained.
- a lithium bis(fluorosulfonyl)imide salt (yield 26%) in a white crystal phase was obtained by the same method described in Example 1 except for adding dropwisely a saturated Li 2 CO 3 suspension (about 14.7 w/v%, 50 mL, 117 mmol) instead of the saturated LiOH ⁇ H 2 O aqueous solution, as the extractor to the second reaction solution.
- the lithium bis(fluorosulfonyl)imide salt thus obtained was identified by 19 F-NMR, and the same spectrum as in Example 1 was obtained.
- a lithium bis(fluorosulfonyl)imide salt (yield 25%) in a white crystal phase was obtained by the same method described in Example 1 except for using LiOH (anhydrous) instead of the saturated LiOH ⁇ H 2 O aqueous solution, as the extractor for the second reaction solution.
- the lithium bis(fluorosulfonyl)imide salt thus obtained was identified by 19 F-NMR, and the same spectrum as in Example 1 was obtained.
- a lithium bis(fluorosulfonyl)imide salt (yield 24%) in a white crystal phase was obtained by the same method described in Example 1 except for using a vessel of a high-density polyethylene material (manufacturer: Thermo Scientific, product name: Nalgene) instead of the vessel of a polypropylene (PP) material (Manufacturer: BD Science, product name: Falcon).
- the lithium bis(fluorosulfonyl)imide salt thus obtained was identified by 19 F-NMR, and the same spectrum as in Example 1 was obtained.
- a lithium bis(fluorosulfonyl)imide salt (yield 25%) in a solid state was obtained by the same method described in Example 1 except for injecting lithium fluoride (2.73 g, 117 mmol).
- the lithium bis(fluorosulfonyl)imide salt thus obtained was identified by 19 F-NMR, and the same spectrum as in Example 1 was obtained.
- a lithium bis(fluorosulfonyl)imide salt (yield 25%) in a solid state was obtained by the same method described in Example 1 except for injecting lithium fluoride (4.25 g, 164 mmol).
- the lithium bis(fluorosulfonyl)imide salt thus obtained was identified by 19 F-NMR, and the same spectrum as in Example 1 was obtained.
- a lithium bis(fluorosulfonyl)imide salt (yield 14%) in a solid state was obtained by the same method described in Example 1 except for injecting lithium fluoride (0.91 g, 35.1 mmol).
- the lithium bis(fluorosulfonyl)imide salt thus obtained was identified by 19F-NMR, and the same spectrum as in Example 1 was obtained.
- a lithium bis(fluorosulfonyl)imide salt (yield 25%) in a solid state was obtained by the same method described in Example 1 except for refluxing while heating for 10 hours during preparing the second reaction solution.
- the lithium bis(fluorosulfonyl)imide salt thus obtained was identified by 19F-NMR, and the same spectrum as in Example 1 was obtained.
- a lithium bis(fluorosulfonyl)imide salt (yield 22%) in a solid state was obtained by the same method described in Example 1 except for refluxing while heating for 3 hours during preparing the second reaction solution.
- the lithium bis(fluorosulfonyl)imide salt thus obtained was identified by 19 F-NMR, and the same spectrum as in Example 1 was obtained.
- a lithium bis(fluorosulfonyl)imide salt (yield 23%) in a solid state was obtained by the same method described in Example 1 except for refluxing while heating for 18 hours during preparing the second reaction solution.
- the lithium bis(fluorosulfonyl)imide salt thus obtained was identified by 19 F-NMR, and the same spectrum as in Example 1 was obtained.
- a lithium bis(fluorosulfonyl)imide salt (yield 16%) in a white crystal phase was obtained by the same method described in Example 1 except for using a round bottom glass flask vessel (manufacturer: Scott-duran) instead of the equipped vessel of a polypropylene (PP) material (manufacturer: BD Science, product name: Falcon), and performing a dehydration process using toluene.
- a round bottom glass flask vessel manufactured by the same method described in Example 1 except for using a round bottom glass flask vessel (manufacturer: Scott-duran) instead of the equipped vessel of a polypropylene (PP) material (manufacturer: BD Science, product name: Falcon), and performing a dehydration process using toluene.
- PP polypropylene
- Example 2 The same method described in Example 1 was performed except for injecting tetrahydrofuran (20 mL, 17.8 g) as the organic solvent for preparing the first reaction solution. However, a lithium bis(fluorosulfonyl)imide salt in a white crystal phase was not obtained.
- Example 2 The same method described in Example 2 was performed except for injecting toluene (20 mL, 17.3 g) as the organic solvent for preparing the first reaction solution. However, a lithium bis(fluorosulfonyl)imide salt in a white crystal phase was not obtained.
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Description
- The present invention relates to a method for preparing a lithium bis(fluorosulfonyl)imide salt, and more particularly, to a method for preparing a lithium bis(fluorosulfonyl)imide salt, which is carried out in one-step reaction to improve processability, and in a vessel of a specific material suppressing side reactions to improve production efficiency.
- Recently, as electric, electronic, communication and computer industries are rapidly developed, demand for secondary batteries having high performance and high stability has been significantly increased. Particularly, depending on trends of miniaturization and weight-lightening of electronic (communication) equipment, the thinning and miniaturizing of a lithium secondary battery which is a key component in these fields, are required.
- As the electrolytes of lithium secondary batteries, ion conductive nonaqueous electrolytes obtained by dissolving electrolyte salts in nonaqueous organic solvents are primarily used.
- Meanwhile, a lithium salt such as LiPF6, which is widely used as the electrolyte salt is a material having low thermal stability and moisture sensitivity, and in case of reacting with water, HF is produced as a by-product due to the hydrolysis of PF6 -. The HF thus produced spontaneously reacts with an electrode active material which shows weak basicity, to elute an electrode active material component. More particularly, if a positive electrode active material reacts with HF, a positive electrode active material component is eluted, of course, and lithium fluoride (LiF) is formed on the surface of the positive electrode to increase electrical resistance in an electrode and generate gas, thereby degrading battery life.
- Recently, in order to solve such problems, study on an electrolyte salt which may replace LiPF6 is on the rise, and a lithium imide salt has been suggested as a typical material.
- Particularly, among the lithium imide salts, as a lithium bis(fluorosulfonyl)imide salt (LiFSI) becomes known to have high thermal stability and humidity safety, low corrosiveness and viscosity, and high electroconductivity, and is known as a material accomplishing excellent performance in high output conditions and at a low temperature, demand thereon is gradually increasing.
- However, despite such advantages, the lithium bis(fluorosulfonyl)imide salt may be prepared via (1) fluoridating reaction of chlorosulfonyl imide or the salt thereof, (2) cation exchange reaction, and (3) contact reaction with an aqueous alkaline solution, in order. Accordingly, the preparation method is a multistep synthetic process and complicated, and thus, the commercialization thereof is difficult considering cost competition when compared with LiPF6.
- In addition, the yield of the lithium bis(fluorosulfonyl)imide salt is also lower when compared with the conventional lithium salts, and the development of a method for preparing a lithium bis(fluorosulfonyl)imide salt with high purity while decreasing the cost for the occupation of the market, is required.
- (Patent Document)
Korean Patent Laid-open Publication No. 2012-0022833 -
CN 106 276 829 A relates to a method for preparing lithium bis(fluorosulfonyl) imide (LiFSI) which comprises dissolving bis(chlorosulfonyl)imide in ethyl acetate and the addition of lithium fluoride.JP 2018-035054 A EP 2 578 533 A1 discloses the preparation of an alkali metal salt of a fluorosulfonyl imide by fluorination of a chlorosulfonyl imide and concentration of the reaction solution while bubbling gas thereinto or by thin film distillation. - An aspect of the present invention to solve the above-described problems is to provide a method for preparing a lithium bis(fluorosulfonyl)imide salt with high purity, by which reaction steps are simplified and side reactions are minimized.
- According to an aspect of the present invention, there is provided a method for preparing a lithium bis(fluorosulfonyl)imide salt, including a step of dissolving bis(chlorosulfonyl)imide in an organic solvent in a non-glass vessel to prepare a first reaction solution; a step of injecting lithium fluoride (LiF) to the first reaction solution in the non-glass vessel and refluxing while heating to prepare a second reaction solution; a step of separating a product including a lithium bis(fluorosulfonyl)imide salt and the organic solvent from the second reaction solution; and a step of obtaining the lithium bis(fluorosulfonyl)imide salt in a solid phase from the product, wherein the organic solvent is at least one or more selected from the group consisting of ethyl acetate, butyl acetate, chloroform, dichloromethane, dichloroethane, benzene, xylene and acetonitrile, wherein the non-glass vessel is formed using at least one or more materials selected from the group consisting of polypropylene (PP), polytetrafluoroethylene (PTFE), high-density polyethylene (HDPE), a perfluoroalkoxy resin (PFA), polyvinylidene difluoride (PVDF), and fluoroethylene propylene (FEP).
- The step of separating the product from the second reaction solution may include a step of cooling the second reaction solution; and a step of injecting an extractor to the cooled second reaction solution to separate the product including the lithium bis(fluorosulfonyl)imide salt and the organic solvent.
- The step of obtaining the lithium bis(fluorosulfonyl)imide salt in a solid phase from the product may include a step of removing the organic solvent from the product for concentration; and a step of drying the concentrated product to obtain the lithium bis(fluorosulfonyl)imide salt in a solid phase.
- In the step of preparing the first reaction solution, the organic solvent may be used in from 200 parts by weight to 1,000 parts by weight with respect to 100 parts by weight of the bis(chlorosulfonyl)imide.
- Meanwhile, in the step of preparing the second reaction solution, the lithium fluoride (LiF) may be injected in 1 mol to 10 mol with respect to 1 mol of the bis(chlorosulfonyl)imide.
- In addition, in the step of preparing the second reaction solution, a time period for the refluxing while heating may be from 2 hours to 20 hours.
- The extractor may include at least one or more selected from the group consisting of LiOH (anhydride), LiOH·H2O, Li2CO3, lithium methoxide (LiOMe), lithium ethoxide (LiOEt) and lithium tert-butoxide (LiOt-Bu).
- The method for preparing a lithium bis(fluorosulfonyl)imide salt according to the present invention may simplify a synthesis process to improve processability when compared with the conventional process, and may save production costs. In addition, since the synthesis reaction is performed in a non-glass vessel, side reactions generated during the reaction in a glass vessel during synthesis reaction may be prevented from happening, and a lithium bis(fluorosulfonyl)imide salt with high purity may be prepared.
-
FIG. 1 is a 19F-NMR spectrum of a lithium bis(fluorosulfonyl)imide salt prepared in Example 1 of the present invention. - Hereinafter, the present invention will be described in more detail.
- It will be understood that words or terms used in the specification and claims shall not be interpreted as the meaning defined in commonly used dictionaries. It will be further understood that the words or terms should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and the technical idea of the invention, based on the principle that an inventor may properly define the meaning of the words or terms to best explain the invention.
- The terms used herein are for the purpose of describing particular example embodiments only and are not intended to limit the present invention. The singular forms are intended to include the plural forms as well, unless the context clearly indicates otherwise.
- It will be understood that the terms "comprise" and/or "comprising," when used in this specification, specify the presence of stated features, steps, elements or the combination thereof, but do not preclude the presence or addition of one or more other features, steps, elements or the combination thereof.
- The method for preparing a lithium bis(fluorosulfonyl)imide salt according to the present invention includes (1) a step of dissolving bis(chlorosulfonyl)imide in an organic solvent in a non-glass vessel to prepare a first reaction solution, (2) a step of injecting lithium fluoride (LiF) to the first reaction solution in the non-glass vessel and refluxing while heating to prepare a second reaction solution, (3) a step of separating a product including a lithium bis(fluorosulfonyl)imide salt and the organic solvent from the second reaction solution, and (4) a step of obtaining the lithium bis(fluorosulfonyl)imide salt in a solid phase from the product. Meanwhile, the organic solvent may be at least one or more selected from the group consisting of ethyl acetate, butyl acetate, chloroform, dichloromethane, dichloroethane, benzene, xylene and acetonitrile. Hereinafter, each step will be explained in detail.
- The step for preparing the first reaction solution is conducted by dissolving bis(chlorosulfonyl)imide in an organic solvent in a non-glass vessel.
- In case of preparing a lithium bis(fluorosulfonyl)imide salt by the conventional method, fluoridation reaction of chlorosulfonyl imide or the salt thereof, cation exchange reaction and contact reaction with an aqueous alkaline solution are all required, and there are problems with its difficult preparation to a degree for commercialization in terms of cost competition.
- Accordingly, recently, there have been attempts to prepare a lithium bis(fluorosulfonyl)imide salt by only fluoridation reaction using lithium fluoride (LiF) injected in step (2), which will be described later, but this method also has limitations relating to the difficult production of a lithium bis(fluorosulfonyl)imide salt in a solid phase.
- Accordingly, in order to solve the problems, the present invention creates a method for preparing a lithium bis(fluorosulfonyl)imide salt in a solid phase with high purity, by which a first reaction solution is prepared in a non-glass vessel and lithium fluoride (LiF) is directly injected into the vessel, and thus, reaction steps are simplified, and side reactions of lithium fluoride (LiF) with silicon (Si) included in a vessel of a glass material is prevented from happening.
- Particularly, the non-glass vessel is formed using at least one or more materials selected from the group consisting of polypropylene (PP), polytetrafluoroethylene (PTFE), high-density polyethylene (HDPE), a perfluoroalkoxy resin (PFA), polyvinylidene difluoride (PVDF), and fluoroethylene propylene (FEP).
- The organic solvent which is the solvent of the first reaction solution may use any solvents which is capable of dissolving bis(chlorosulfonyl)imide without inducing side reactions with the bis(chlorosulfonyl)imide, typically, at least one or more selected from the group consisting of ethyl acetate, butyl acetate, chloroform, dichloromethane, dichloroethane, benzene, xylene and acetonitrile may be used.
- However, as the organic solvent, an organic solvent such as tetrahydrofuran (THF) and toluene is not used, because these solvents may participate in the reaction and induce side reactions, and may inhibit the substitution reaction of the bis(chlorosulfonyl)imide and hinder the production of a lithium bis(fluorosulfonyl)imide salt.
- The organic solvent may be included in 200 parts by weight to 1,000 parts by weight, preferably, 300 parts by weight to 700 parts by weight, more preferably, 300 parts by weight to 500 parts by weight with respect to 100 parts by weight of the bis(chlorosulfonyl)imide. A case of including the organic solvent in the range, is advantageous considering the reaction rate and cost.
- In this case, the time period of the step for preparing the first reaction solution is set to a time period for sufficiently dissolving the bis(chlorosulfonyl)imide in the organic solvent without precipitation, and the first reaction solution may be prepared within 10 hours or less, more particularly, from 10 minutes to 2 hours.
- Next, the step for preparing the second reaction solution will be explained. The second reaction solution is prepared by injecting lithium fluoride (LiF) in a non-glass vessel in which the first reaction solution has been prepared, and refluxing while heating.
-
- the reactants, bis(chlorosulfonyl)imide (SO2Cl)2NH) and lithium fluoride (LiF), react to produce a lithium bis (fluorosulfonyl) imide salt ((SO2F)2N-Li+).
- More particularly, since the reaction undergoes a refluxing while heating process, though a separate catalyst is not used, a chlorine atom (Cl) of the bis(chlorosulfonyl)imide may be substituted with a fluorine atom (F) of lithium fluoride (LiF) by heat. In addition, the lone pair of a nitrogen atom (N) contained in the bis(chlorosulfonyl)imide reacts with a lithium atom (Li) of lithium fluoride (LiF) to produce a lithium bis(fluorosulfonyl)imide salt. In this case, the hydrogen of the bis(chlorosulfonyl)imide and the fluorine of the lithium fluoride (LiF) may partially react to produce hydrogen fluoride (HF). Through the reaction, the second reaction solution is prepared.
- Meanwhile, during preparing the second reaction solution, the lithium fluoride (LiF) may be included in 1 mol to 10 mol, preferably, 1.8 mol to 10 mol, more preferably, 1.9 mol to 10 mol with respect to 1 mol of the bis(chlorosulfonyl)imide. If an excessive amount of the lithium fluoride (LiF) remains after finishing the reaction, side reactions may be induced and the lithium fluoride (LiF) is required to be removed after finishing the reaction. However, the removal of remaining lithium fluoride is a difficult process and costs high.
- Accordingly, the lithium fluoride (LiF) is preferably in the range to perform sufficient reaction of the bis(chlorosulfonyl)imide, and to minimize the amount of remaining lithium fluoride (LiF) after finishing the reaction, thereby preventing side reactions from happening and increasing processability and reaction efficiency.
- In the reaction process, the refluxing heating process may be performed while keeping the temperature to the boiling point of the organic solvent used or higher for from 2 hours to 20 hours, particularly, from 5 hours to 20 hours, more particularly, from 5 hours to 15 hours.
- The temperature conditions of the refluxing heating process may be changed according to the kind of the organic solvent used, and if the refluxing heating process is carried out in the time period range, the reaction may be sufficiently carried out, and the production of by-products due to side reactions may be prevented.
- Next, a product including the lithium bis(fluorosulfonyl)imide salt and the organic solvent is separated from the second reaction solution. The step of separating the product from the second reaction solution includes 1) a step of cooling the second reaction solution and 2) a step of injecting an extractor to the cooled second reaction solution to separate the product including the lithium bis(fluorosulfonyl)imide salt and the organic solvent.
- First, 1) the cooling step is a step for cooling the second reaction solution after finishing the reaction to room temperature or less, so that additional side reactions may not arise due to remaining heat after finishing the refluxing heating process, which is performed for the preparation of the second reaction solution. In this case, the room temperature means the annual mean temperature or the atmospheric temperature, particularly, the temperature in a range of 20±5°C.
- Next, 2) the separating step of the product is a step of injecting an extractor to the cooled second reaction solution, and is a step of neutralizing the second reaction solution which is in a strongly acidic state as well as removing hydrogen fluoride (HF) produced as by-products during carrying out the reaction, and of separating the product including the lithium bis(fluorosulfonyl)imide salt and the organic solvent.
- As the extractor, a lithium-containing basic compound may be used, and typical examples may include at least one or more selected from the group consisting of LiOH (anhydride), LiOH·H2O, Li2CO3, lithium methoxide (LiOMe), lithium ethoxide (LiOEt) and lithium tert-butoxide (LiOt-Bu). In this case, if the lithium-containing basic compound is an insoluble solid in an organic solvent, such as (saturated) LiOH and (saturated) Li2CO3, the insoluble solid may be dissolved in water and injected in an aqueous solution state.
- The extractor may be included in 1 mol to 10 mol, preferably, 2 mol to 7 mol, more preferably, 3 mol to 6 mol with respect to 1 mol of the bis(chlorosulfonyl)imide. If the extractor in included in the range, a strongly acidic reaction solution may be neutralized, and impurities may be removed to produce a product with high purity.
- By injecting the extractor, the hydrogen fluoride (HF) may be neutralized and separated from the product including the lithium bis(fluorosulfonyl)imide salt and the organic solvent, and may be easily removed in a subsequent extracting step of the organic solvent. After injecting the extractor, if the reaction solution is stirred at a temperature of room temperature or less, particularly, under temperature conditions of -10°C to 10°C for 30 minutes to 3 hours, the lithium bis(fluorosulfonyl)imide salt may be extracted by an organic solvent.
- In case of using a compound capable of being dissolved in an organic solvent as the extractor, the compound produced as by-products reacts with hydrogen fluoride (HF) to produce an insoluble salt, and an organic layer may be separated through filtering.
- If an extractor in an aqueous solution state is used as the extractor, the second reaction solution into which the extractor is injected, is injected into a separating funnel, an organic solvent layer including the product and an aqueous layer in which hydrogen fluoride (HF) and the extractor are dissolved, are separated, and the separated organic solvent layer may be recovered.
- Finally, the step of obtaining the lithium bis(fluorosulfonyl)imide salt in a solid phase from the product will be explained. In order to obtain the lithium bis(fluorosulfonyl)imide salt in a solid phase, 1) a step of removing the organic solvent from the product for concentration, and 2) a step of drying the concentrated product to obtain a lithium bis(fluorosulfonyl)imide salt in a solid phase are included.
- Step 1) and step 2), both are steps for improving the yield of the lithium bis(fluorosulfonyl)imide salt in a solid phase, and first, step 1) is a step for removing the organic solvent from the product. In order to remove the organic solvent, a method of concentrating at a low temperature in a reduced pressure, or a method of distilling by heating in an atmospheric pressure may be applied. However, the method is not limited to the illustrated methods, and any methods for improving the yield of the lithium bis(fluorosulfonyl)imide salt in a solid phase may be used as long as side reactions with the product are not induced and the organic solvent may be removed.
- Meanwhile, the step of drying the product concentrated after step 1) is a step of drying the product in vacuum or in an environment blocked from the air. Drying processes generally used may be applied, and for example, a method of drying by applying heat in vacuum or a method of drying in a sealed desiccator may be used. Through the drying step, the lithium bis(fluorosulfonyl)imide salt in a solid phase may be obtained.
- According to the above-described preparation method of the present invention, high yield may be achieved when compared with the conventional method. Particularly, the yield of the lithium bis(fluorosulfonyl)imide salt was only 160 or less by the conventional preparation method of the lithium bis(fluorosulfonyl)imide salt, but by using the method of the present invention, the lithium bis(fluorosulfonyl)imide salt in a solid phase may be obtained in a yield of at least 210 or higher.
- Hereinafter, embodiments of the present invention will be described in detail for particularly explaining the present invention. However, the embodiments according to the present invention may be changed into various other types, but should not be interpreted to limit the scope of the present invention to the embodiments. The embodiments of the present invention are provided only for more complete explanation of the present invention to a person having an average knowledge in the art.
- To a vessel (manufacturer: BD Science, product name: Falcon) of a polypropylene (PP) material, equipped with a magnetic stirring bar, a reflux condenser and a thermometer, ethyl acetate (20 mL, 18.0 g) was injected as an organic solvent, and then, bis(chlorosulfonyl)imide (5.00 g, 23.4 mmol) was injected thereto and dissolved to prepare a first reaction solution.
- Then, lithium fluoride (1.21 g, 46.8 mmol) was injected while stirring the first reaction solution at room temperature, and in a sealed state, refluxing while heating was carried out for 6 hours to prepare a second reaction solution. After finishing the reaction, the second reaction solution was cooled to room temperature (25°C), and a saturated LiOH·H2O aqueous solution (about 25 w/v%, 20 mL, 119 mmol) was added thereto dropwisely as an extractor while stirring, and the resultant solution was stirred for 30 minutes at a temperature or room temperature or less (-10°C to 15°C).
- Next, the second reaction solution containing the extractor was poured to a separating funnel to separate an organic solvent layer containing the product and an aqueous layer containing hydrogen fluoride (HF). The organic solvent layer thus separated was recovered. The organic solvent layer thus recovered was concentrated in reduced pressure conditions until obtaining a semi-solid state. Then, an organic solvent layer residue in the semi-solid state was dried further in vacuum at room temperature for 1 hour or more to obtain a lithium bis(fluorosulfonyl)imide salt (yield 25%) in a white crystal phase. The lithium bis(fluorosulfonyl)imide salt thus obtained was identified by 19F-NMR (19F-NMR (470 MHz, CD3CN): δ 51.062 (s)) (see
FIG. 1 ), and as a result, the purity was 99% or more and impurities were not found. - A lithium bis(fluorosulfonyl)imide salt (yield 210) in a white crystal phase was obtained by the same method described in Example 1 except for using acetonitrile (20 mL, 15.7 g) as the organic solvent during preparing the first reaction solution. The lithium bis(fluorosulfonyl)imide salt thus obtained was identified by 19F-NMR, and the same spectrum as in Example 1 was obtained.
- A lithium bis(fluorosulfonyl)imide salt (yield 26%) in a white crystal phase was obtained by the same method described in Example 1 except for adding dropwisely a saturated Li2CO3 suspension (about 14.7 w/v%, 50 mL, 117 mmol) instead of the saturated LiOH·H2O aqueous solution, as the extractor to the second reaction solution. The lithium bis(fluorosulfonyl)imide salt thus obtained was identified by 19F-NMR, and the same spectrum as in Example 1 was obtained.
- A lithium bis(fluorosulfonyl)imide salt (yield 25%) in a white crystal phase was obtained by the same method described in Example 1 except for using LiOH (anhydrous) instead of the saturated LiOH·H2O aqueous solution, as the extractor for the second reaction solution. The lithium bis(fluorosulfonyl)imide salt thus obtained was identified by 19F-NMR, and the same spectrum as in Example 1 was obtained.
- A lithium bis(fluorosulfonyl)imide salt (yield 24%) in a white crystal phase was obtained by the same method described in Example 1 except for using a vessel of a high-density polyethylene material (manufacturer: Thermo Scientific, product name: Nalgene) instead of the vessel of a polypropylene (PP) material (Manufacturer: BD Science, product name: Falcon). The lithium bis(fluorosulfonyl)imide salt thus obtained was identified by 19F-NMR, and the same spectrum as in Example 1 was obtained.
- A lithium bis(fluorosulfonyl)imide salt (yield 25%) in a solid state was obtained by the same method described in Example 1 except for injecting lithium fluoride (2.73 g, 117 mmol). The lithium bis(fluorosulfonyl)imide salt thus obtained was identified by 19F-NMR, and the same spectrum as in Example 1 was obtained.
- A lithium bis(fluorosulfonyl)imide salt (yield 25%) in a solid state was obtained by the same method described in Example 1 except for injecting lithium fluoride (4.25 g, 164 mmol). The lithium bis(fluorosulfonyl)imide salt thus obtained was identified by 19F-NMR, and the same spectrum as in Example 1 was obtained.
- A lithium bis(fluorosulfonyl)imide salt (yield 14%) in a solid state was obtained by the same method described in Example 1 except for injecting lithium fluoride (0.91 g, 35.1 mmol). The lithium bis(fluorosulfonyl)imide salt thus obtained was identified by 19F-NMR, and the same spectrum as in Example 1 was obtained.
- A lithium bis(fluorosulfonyl)imide salt (yield 25%) in a solid state was obtained by the same method described in Example 1 except for refluxing while heating for 10 hours during preparing the second reaction solution. The lithium bis(fluorosulfonyl)imide salt thus obtained was identified by 19F-NMR, and the same spectrum as in Example 1 was obtained.
- A lithium bis(fluorosulfonyl)imide salt (yield 22%) in a solid state was obtained by the same method described in Example 1 except for refluxing while heating for 3 hours during preparing the second reaction solution. The lithium bis(fluorosulfonyl)imide salt thus obtained was identified by 19F-NMR, and the same spectrum as in Example 1 was obtained.
- A lithium bis(fluorosulfonyl)imide salt (yield 23%) in a solid state was obtained by the same method described in Example 1 except for refluxing while heating for 18 hours during preparing the second reaction solution. The lithium bis(fluorosulfonyl)imide salt thus obtained was identified by 19F-NMR, and the same spectrum as in Example 1 was obtained.
- A lithium bis(fluorosulfonyl)imide salt (yield 16%) in a white crystal phase was obtained by the same method described in Example 1 except for using a round bottom glass flask vessel (manufacturer: Scott-duran) instead of the equipped vessel of a polypropylene (PP) material (manufacturer: BD Science, product name: Falcon), and performing a dehydration process using toluene.
- The same method described in Example 1 was performed except for injecting tetrahydrofuran (20 mL, 17.8 g) as the organic solvent for preparing the first reaction solution. However, a lithium bis(fluorosulfonyl)imide salt in a white crystal phase was not obtained.
- The same method described in Example 2 was performed except for injecting toluene (20 mL, 17.3 g) as the organic solvent for preparing the first reaction solution. However, a lithium bis(fluorosulfonyl)imide salt in a white crystal phase was not obtained.
Claims (7)
- A method for preparing a lithium bis(fluorosulfonyl)imide salt, the method comprising:a step of dissolving bis(chlorosulfonyl)imide in an organic solvent in a non-glass vessel to prepare a first reaction solution;a step of injecting lithium fluoride (LiF) to the first reaction solution in the non-glass vessel, and refluxing while heating to prepare a second reaction solution;a step of separating a product including a lithium bis(fluorosulfonyl)imide salt and the organic solvent from the second reaction solution; anda step of obtaining the lithium bis(fluorosulfonyl)imide salt in a solid phase from the product,wherein the organic solvent is at least one or more selected from the group consisting of ethyl acetate, butyl acetate, chloroform, dichloromethane, dichloroethane, benzene, xylene and acetonitrile,and the non-glass vessel is formed using at least one or more materials selected from the group consisting of polypropylene (PP), polytetrafluoroethylene (PTFE), high-density polyethylene (HDPE), a perfluoroalkoxy resin (PFA), polyvinylidene difluoride (PVDF), and fluoroethylene propylene (FEP).
- The method for preparing a lithium bis(fluorosulfonyl)imide salt according to claim 1, wherein the step of separating the product from the second reaction solution comprises:a step of cooling the second reaction solution; anda step of injecting an extractor to the cooled second reaction solution to separate the product comprising the lithium bis(fluorosulfonyl)imide salt and the organic solvent.
- The method for preparing a lithium bis(fluorosulfonyl)imide salt according to claim 1, wherein the step of obtaining the lithium bis(fluorosulfonyl)imide salt in a solid phase from the product comprises:a step of removing the organic solvent from the product for concentration; anda step of drying the concentrated product to obtain the lithium bis(fluorosulfonyl)imide salt in a solid phase.
- The method for preparing a lithium bis(fluorosulfonyl)imide salt according to claim 1, wherein in the step of preparing the first reaction solution, the organic solvent is used in from 200 parts by weight to 1,000 parts by weight with respect to 100 parts by weight of the bis(chlorosulfonyl)imide.
- The method for preparing a lithium bis(fluorosulfonyl)imide salt according to claim 1, wherein in the step of preparing the second reaction solution, the lithium fluoride (LiF) is injected in 1 mol to 10 mol with respect to 1 mol of the bis(chlorosulfonyl)imide.
- The method for preparing a lithium bis(fluorosulfonyl)imide salt according to claim 1, wherein in the step of preparing the second reaction solution, a time period for the refluxing while heating is from 2 hours to 20 hours.
- The method for preparing a lithium bis(fluorosulfonyl)imide salt according to claim 2, wherein the extractor comprises at least one or more selected from the group consisting of LiOH (anhydride), LiOH·H2O, Li2CO3, lithium methoxide (LiOMe), lithium ethoxide (LiOEt) and lithium tert-butoxide (LiOt-Bu).
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PCT/KR2019/004186 WO2019199013A1 (en) | 2018-04-10 | 2019-04-09 | Method for preparing lithium bis(fluorosulfonyl)imide salt |
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US (1) | US11618687B2 (en) |
EP (1) | EP3750848B1 (en) |
JP (1) | JP6921464B2 (en) |
KR (1) | KR102288298B1 (en) |
CN (1) | CN111527045A (en) |
ES (1) | ES2971840T3 (en) |
HU (1) | HUE065881T2 (en) |
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CN112624067A (en) * | 2021-01-14 | 2021-04-09 | 山东大学 | Green and simple preparation method of lithium bis (fluorosulfonyl) imide |
CN113603069A (en) * | 2021-10-08 | 2021-11-05 | 江苏华盛锂电材料股份有限公司 | Method for removing trace impurities in lithium bis (fluorosulfonyl) imide |
CN116495711A (en) * | 2022-01-19 | 2023-07-28 | 湖南福邦新材料有限公司 | Lithium bis (fluorosulfonyl) imide composition and preparation method thereof |
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FR2818972B1 (en) * | 2000-12-29 | 2003-03-21 | Rhodia Chimie Sa | PROCESS FOR FLUORINATION OF A HALOGEN COMPOUND |
JP4705476B2 (en) | 2006-01-10 | 2011-06-22 | 第一工業製薬株式会社 | Method for producing fluorine compound |
JP5208782B2 (en) * | 2009-01-22 | 2013-06-12 | 株式会社日本触媒 | Fluorosulfonylimides and process for producing the same |
CN102046523A (en) * | 2008-07-23 | 2011-05-04 | 第一工业制药株式会社 | Process for producing bis(fluorosulfonyl)imide anion compound, and ion-pair compound |
KR101345271B1 (en) | 2009-11-27 | 2013-12-27 | 가부시기가이샤 닛뽕쇼꾸바이 | Fluorosulfony limide salt and method for producing fluorosulfonyl imide salt |
EP3778473B1 (en) * | 2010-05-28 | 2023-07-05 | Nippon Shokubai Co., Ltd. | Alkali metal salt of fluorosulfonyl imide |
EP3170789B1 (en) * | 2011-03-03 | 2018-04-18 | Nippon Soda Co., Ltd. | Production process for fluorosulfonylimide ammonium salt |
FR2975694B1 (en) | 2011-05-24 | 2013-08-02 | Arkema France | PROCESS FOR THE PREPARATION OF BIS (FLUOROSULFONYL) IMIDURE OF LITHIUM |
KR101119625B1 (en) * | 2011-06-30 | 2012-03-07 | 한국에너지기술연구원 | Advance purification methods for betulonic acid and boc-lysinated betulonic acid, and organic synthesis of betulonic acid amides with piperazine derivatives |
KR101718292B1 (en) | 2015-11-26 | 2017-03-21 | 임광민 | Novel method for preparing lithium bis(fluorosulfonyl)imide |
KR101800299B1 (en) * | 2016-01-08 | 2017-11-22 | 건국대학교 글로컬산학협력단 | Method for preparing lithium fluorosulfonylimide using alcohol solvents |
CN107226461B (en) * | 2016-03-25 | 2020-12-18 | 浙江省化工研究院有限公司 | Preparation method of bis (fluorosulfonyl) imide salt |
JP6916666B2 (en) * | 2016-05-26 | 2021-08-11 | 株式会社日本触媒 | Method for producing bis (fluorosulfonyl) imide alkali metal salt and bis (fluorosulfonyl) imide alkali metal salt composition |
CN109415209B (en) | 2016-05-27 | 2022-09-27 | 株式会社日本触媒 | Process for producing bis (fluorosulfonyl) imide alkali metal salt |
CN106276829B (en) * | 2016-08-23 | 2018-08-07 | 荣成青木高新材料股份有限公司 | A kind of synthetic method of double fluorine sulfimide lithiums |
US20220359921A9 (en) * | 2018-11-30 | 2022-11-10 | Makita Corporation | Battery pack |
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EP3750848A1 (en) | 2020-12-16 |
KR102288298B1 (en) | 2021-08-11 |
CN111527045A (en) | 2020-08-11 |
ES2971840T3 (en) | 2024-06-10 |
JP6921464B2 (en) | 2021-08-18 |
KR20190118525A (en) | 2019-10-18 |
US20200392010A1 (en) | 2020-12-17 |
US11618687B2 (en) | 2023-04-04 |
HUE065881T2 (en) | 2024-06-28 |
EP3750848A4 (en) | 2021-06-09 |
PL3750848T3 (en) | 2024-05-20 |
WO2019199013A1 (en) | 2019-10-17 |
JP2021505510A (en) | 2021-02-18 |
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